2-ureido-benzamides their production and use

ABSTRACT

2-UREIDO-BENZAMIDES OF THE FORMULA   1-(H2N-CO-),2-(R3-N(-R4)-CO-N(-R2)-),(R1)N-BENZENE   WHEREIN   R1 REPRESENTS HALOGEN, LOWER ALKYL OR LOWER ALKOXY OF AT MOST 5 CARBON ATOMS, R2 REPRESENTS HYDROGEN OR LOWER ALKYL OF AT MOST 5 CARBON ATOMS, R3 REPRESENTS HYDROGEN, LOWER ALKYL OR LOWER ALKOXY OF AT MOST 5 CARBON ATOMS, R REPRESENTS AN ALKYL, ALKENYL OR ALKINYL RADICAL WITH AT MOST 8 CARBON ATOMS, LOWER HALOGEN-ALKYL, ALKOXYALKYL OR ALKYLMERCAPTOALKYL OF AT MOST 5 CARBON ATOMS OR CYCLOALKYL HAVING 3 TO 10 CARBON ATOMS AS RING MEMBERS, AND N REPRESENTS A WHOLE NUMBER FROM 0 TO 3,   ARE DISCLOSED AS HERBICIDALLY ACTIVE COMPOUNDS OF ENHANCED TOXICITY TO UNDESIRABLE PLANT GROWTH AND IMPROVED SELECTIVITY. A METHOD OF CONTROLLING UNDESIRABLE PLANT GROWTH WITH SUCH COMPOUNDS AND COMPOSITIONS CONTAINING THEM AS ACTIVE INGREDIENTS ARE ALSO DISCLOSED.

3,646,136 2-URElDO-BENZAMIDES, THEIR PRODUCTION AND USE Karl Hoegerle, Basel, Switzerland, Jean-Claude Muller, St. Louis, France, and Christian Vogel and Jurg Rumpf, Binningen, near Basel, Switzerland, assignors to Geigy Chemical Corporation, Ardsley, N.Y.

No Drawing. Filed Mar. 24, 1969, Ser. No. 809,978 Claims priority, application Switzerland, Mar. 29, 1968, 4,710/ 68 Int. Cl. C07c 127/00 US. Cl. 260553 A 2 Claims ABSTRACT OF THE DISCLOSURE 2-ureido-benzamides of the formula @0115, (EFF? My C Y H- r\\ wherein are disclosed as herbicidally active compounds of enhanced toxicity to undesirable plant growth and improved selectivity. A method for controlling undesirable plant growth with such compounds and compositions containing them as active ingredients are also disclosed.

DESCRIPTION OF THE INVENTION The present invention concerns herbicidal Z-ureidobenzamides, processes for the production thereof, a method for controlling undesirable plant growth with the aid of the Z-ureido-benzamides as well as compositions containing the herbicidally active substances.

More particularly, the invention provides Z-ureido-benzamides of the general Formula I C ONHg (R1) 1.

R2 0 R4 (I) wherein R represents halogen, lower alkyl or lower alkoxy of at most 5 carbon atoms,

R represents hydrogen or lower alkyl of at most 5 carbon atoms,

R represents hydrogen, lower alkyl or lower alkoxy of at most 5 carbon atoms,

R represents an alkyl, alkenyl or alkinyl radical with at most 8 carbon atoms, lower halogen-alkyl, alkoxyalkyl or alkylmercaptoalkyl of at most 5 carbon atoms or cycloalkyl having 3 to 10 carbon atoms as ring member, and

11 represent a whole number from 0 to 3,

which are useful in the control of undesirable plant growth, especially in the control of weeds and wild grasses.

United States Patent As lower halogen-alkyl radical R represents an alkyl radical having 1 to 5 carbon atoms, as previously stated, which may be monoor poly-substituted by fluorine, chlorine and/or bromine. The alkyl radical R is either a straight chained alkyl radical having 1 to 8 carbon atoms or a branch chained alkyl radical having 3 to 8 carbon atoms; the alkenyl radical R; has 2 to 4 carbon atoms and is especially the allyl or methallyl radical; and as alkynyl radical, R, has 2 to 5 carbon atoms, and in particular is the propynyl or l-methyl-2-propynyl radical.

As a cycoalkyl radical, R represents either a monocyclic or a polycyclic radical, eg the cyclopropyl, 1- methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl radical, or bicyclooctyl, tricyclononyl, tetracyclononyl, octyhydromethenopentylanyl radicals etc. The alkyl moiety in the alkoxy and alkylthio groupings has 1 to 5 carbon atoms in the normal chain or 3 to 5 carbon atoms in the branched chain. As halogen, R denotes fluorine, or bromine.

The Z-ureido-benzamides of the Formula I are produced by reacting a benzamide of the Formula II wherein Hal represents halogen up to atomic number 35, or (b) with the formation components of a carbamic acid halide of the Formula III, namely phosgene and an amine of the Formula 1V,

in an inert solvent or diluent and in the presence of a condensation agent. According to a variation of the process of the invention, Z-ureido benzamides of the Formula I, wherein R represents hydrogen, are obtained by reacting a benzamide of the Formula II with an isocyanate of the Formula V:

R NCO (V) or with a mixture of the isocyanate with a corresponding carbamic acid halide of the Formula III, optionally in the presence of a condensation agent. In the Formulae II to V, the symbols R to R and n have the meanings given under Formula I.

The reactions are performed in the presence of solvents or diluents which are inert to the reactants. Suitable for this purpose are hydrocarbons such as benzene, toluene, xylols, ether and ethereal compounds such as dialkylether, dioxane, tetrahydrofuran, N,N-di-substituted carboxylic acid amides such as dialkyl formamide and dialkyl acet amide, nitriles such as acetonitrile, chlorinated hydrocarbons such as chlorobenzene, chloroform and methylene chloride.

The reactions, according to the invention, with a carbamic acid halide are carried out, advantageously, in the presence of a basic condensation agent, eig. a tertiary amine such as trialkylamine, pyridine or collidine, or in the presence of an inorganic base, e.g. an alkali metal hydroxide, acetate, hydrogen carbonate, carbonate or phosphate.

Another process for the production of the Z-ureidobenzamides of Formula I comprises heating in an aqueous alkaline medium a Z-cyano-phenylurea of Formula VI,

wherein R and n have the meaning given under Formula I, with an amine of Formula IV. The reaction takes place advantageously in a solvent that is inert to both reactants, such as benzene, toluene, xylene ether.

The new 2-ureido benzamides of the Formula I are crystalline. They possess excellent herbicidal properties and can be used in both pre-emergence and post-emergence applications for controlling weeds and wild grasses.

Tests have shown that the new active substances in suitable concentrations can be used for controlling monocotyl and dicotyl field weeds, e.g. the following: species of millet (panicum sp.), species of mustard (sinapis sp.), species of goosefoot (chenopodiaceaen), also panicle grass (poa annua), foxtail (alopecurus agrestis), camomile (matricaria), parsnip (pastinaca sativa L.) etc., whereby the useful plants such as grain, maize, root vegetables, oil plants, vegetables, cotton, sorghum, soya. beans and lucerneare not impaired in germination and in growth.

The herbicidal activity of the compounds of general Formula I is demonstrated by the following experiment:

A 10% suspension of the active substance was mixed with garden soil so that a final concentration of 0.5 g. of active substance per liter soil was attained. The earth was then placed in pots with the following test plants: rye, mustard, rye grass, sugar-beet, cucumber, cotton,

'vetch and maize. The pots were then put in a green house and kept at a temperature of 2024 C. and 70% relative humidity in continuous daylight. After 20 days the test results were evaluated according to a 10 point scale 10=plants unaffected as control O=plants destroyed 91=intermediate stages of damage.

The 10% suspension was prepared from a wettable powder of the following composition: 10 parts of active substance, 0.6 part of sodium dibutylnaphthyl sulphonate, 10 parts of sodium aluminium silicate, 78.4 points of kaolin and 1 part of a condensate of naphthaline sulphonic acidxphend sulphonic acid:formaldehyde 3:221, which was diluted q.s. with water (all parts are by weight).

The table shows that these compounds are well suited for combating monooctyl and dicotyl weeds in pre-emergence application.

The Z-ureido benzamides of Formula I, mixed together with the usual additives, are used as herbicidal agents. Furthermore, the active substances can be mixed with fertilisers and applied in this form. The range of activity of the benzamides of the invention can be widened by applying them in admixture with other herbicides, eg with triazines such as halogendiamino-s-triazines, alkoxy and alkylthiodiamono-s-triazines, diazines such as uracils, pyridazines, phenols, aliphatic carboxylic acids and halogen carboxylic acids, halogenated benzoic acids and halogenated phenylacetic acids, aryloxyal'kane carboxylic acids and aryloxyalkane sulphonic acids, pyridine carboxylic acids, amides, thioamides, hydrozides, esters and nitriles of similar carboxylic acids, carbamic acid esters and thiocarbamic acid esters, quaternary ammonium compounds, ureas, inorganic salts etc., specially with:

2-chloro-4,6-bisethylamino -s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-'bis- (methoxypropylamino) -s-triazine 2-me thoxy-4, 6-bis- (iso pro pylamino -s-triazine Z-methylmercapto-4-methoxypropylamino-isopropylamino-s-triazine 2-methylmercapto-4,6-bis(isopropylamino)-s-triazine 2-methylmercapto-4,6-bis- (ethylamino -s-triazine Z-methylmercapto-4-ethylamino-6-isopropylamino-striazine 2-methoxy-4,-6-bis-(ethylamino)-s-triazine, 2-methoXy-4-ethylamino-G-isopropylamino-striazine, 2-chloro-4,6-bisisopropylamino -s-triazine, 5-bromo-3-sec.butyl-6-methyl-uracil, 3-cyclohexyl-5,-6-trimethylene-uracil, 5 -amino-5-chloro-l-phenyl-pyridazone- 6) 3,6dioxo-1,2,3,6-tetrahydropyridazine, Dinitro-sec.butylphenol and salts thereof, Pentachlorophenol and salts thereof, Trichloroacetic acid and salts thereof, 2,2-dichloropropionic acid and salts thereof, 2-chloro-N,N-diallylacetic acid amide, N-(3,4'-dichlorophenyl)-cyclopropane carboxylic acid amide, Maleic acid hydrazide, 2,3,6-trichlorobenzoic acid and salts thereof, 2,3,5,6-tetrachlorobenzoic acid and salts thereof, 2-methoxy-3,5,-6-trichlorobenzoic acid and salts thereof, 2-methoxy-3,o-dichlorobenzoic acid and salts thereof, 3-amino-2,S-dichlorobenzoic acid and salts thereof, 3-nitro-2,S-dichlorobenzoic acid and salts thereof, 2-methy1-3,S-dichlorobenzoic acid and salts thereof, Z-methyl-3,5-dichlorobenzoic acid and salts thereof, 2,6-dichlorobenzonitrile, 2,G-dichIoro-thidbenzamide, 2,3,-6-trichlorophenyl acetic acid and salts thereof, 2,4-dihclorophenoxyacetic acid and salts thereof, 2,4,S-trichlorophenoxyacetic acid and salts and esters thereof, (2-methyl-4-chlorophenoxy)-acetic acid and salts and esters thereof, 2-(2',4',5-trichlorophenoxy)-propi-onic acid and salts and esters thereof,

Compound Rye- Rye grass Mustard Sugar beet Cucumber Cotton Vetch Maize 2-( N -methyl-ureido) -honzamide 2-(N,N-dimethyl-ureldo) -benza.mide 2-(N-ethyl-ureido) -benzamide 2-(N-n-propyl-u.reido) -benzaruide- 2-(N-isopropyl-ureido) -benzamide 2- (N -n-butyl-ureido) -b enzamide.

2-(N'-2-methoxyethyl-ureido)-benzamide 2-(N-cycl0propyl-ureido benzarm'de OWCOCOQOOOG CCOCOOOOQQI-c 2-(2',4,5'-trichlorophenoxy)-ethyl-2,2-dichloropropionate, 4-(2',4-dichlorophenoxy)-butyric acid and salts and esters thereof, 4-(2-methyl-4-chlorophenoxy)-butyric acid and salts and esters thereof, 2,3,6-trichlorobenzyloxypropanol, 4-amino-3,5,6-trichloropicolinic acid, -N'-cyclooctyl-N,N-dimethyl urea, 3-phenyl-1,l-dimethyl.- urea, 3-(4'-chlorophenyl)-1,1-dimethyl urea, 3-(3-trifluoromethylphenyl)-1,l-dimethyl urea, 3(3',4-dichlorophenyl)-1,1-dimethyl urea, 3- (3 ',4'-dichlorophenyl l-n-butyll-methyl urea, 3-(3,4-dichlorophenyl)-l,l,3-trimethyl urea, 3-(3,4'-dichlorophenyl)-1,l-diethyl urea, 3-(4'-chlorophenyl)-1-methoxy-l-methyl urea, -3-(3,4-dichlorophenyl)-1-methoxy-l-methyl urea, 3-(4-bromophenyl)-1-methoxy-1-methyl urea, 3-(3',4-dichlorophenyl)-3-methoxya1,1-dimethyl urea, 3-(4'-chlorophenoxy-phenyl)-1,1-dirnethyl urea, N,N-di-(n-propyl)-S-ethyl-thiolcarbamic acid ester, N,N-di-(n-propyl)-S-n-propyl-thiolcarbamic acid ester, N-ethyl-N-(n-butyl)-S-n-propyl-thiolcarbamic acid ester, N-phenyl-O-isopropyl-carbamic acid ester, N-(m-chlorophenyl)-O-isopropyl-carbamic acid ester, N-(m-chlorophenyl)-O-(4'-chloro-2butinyl)-carbamic acid ester, N- (3 ',4-dichlorophenyl) -Omethyl-carbamic acid ester.

The following examples illustrate the production processes for the compounds of Formula I. Where not otherwise expressly stated, the temperatures are given in degrees centigrade.

EXAMPLE 1 5.7 g. of methyl isocyanate are added dropwise at room temperature (25) to a solution of 13.6 g. of anthranilic acid amide in 100 ml. of acetonitrile. The reaction mixture is then heated, while stirring, for half an hour at 50. After cooling, the precipitate is filtered oil and recrystallised from methanol. The thus obtained 2-(N'-methy1- ureido)-benzamide has a melting point of 191 (decomposition).

EXAMPLE 2 A solution of 27.2 g. of anthranilic acid amide and 30 g. of triethylamine in 200 ml. of absolute toluene is refiuxed to boiling and is then mixed dropwise with 32 g. of dimethylcarbamic acid chloride. The reaction mixture is then refluxed for a further hour. The precipitate obtained after cooling is filtered off and is slurried in water. After recrystallising from isopropanol, the obtained 2-(N,N-dimethyl-ureido)-benzamide had a melting point of 185- 186 (decomposition).

EXAMPLE 3 50 ml. of an aqueous hydrogen peroxide solution are added dropwise during 30 minutes at a temperature of to to a solution of 5.1 g. of 2-(N-methoxy-N-methylureido)-benzonitrile in ml. of acetone. By adding 1 ml. of 2 N sodium hydroxide solution the pH of the reaction mixture is kept between 8 and 9. The mixture is stirred for 12 hours at room temperature and the precipitate formed is filtered. The 2-(N'-methoxy-N'-methyl-ureido)- benzamide thus obtained melts at l'8ll83 (decomposition).

The 2-(N'-methoxy-N'-methyl-ureido)-benzonitrile used as starting material is obtained as follows:

A solution of 10.5 g. of 2-cyano-phenyl-isocyanate in 60 ml. of benzene is added at a temperature of 10l5 to another solution of 4.9 g. of N-methoxy-N-methylamine in 40 ml. of benzene. The solvent is then removed under vacuo and the residue is recrystallised from hexane. Thus 2-(N-methoxy-N'-methyl-ureido) benzonitrile having a M.P. of 71-72 is obtained.

In the ways described in the previous examples, the

2-ureido benzamides listed in the following table are obtained:

4-chloro-2AN-n-propyl-ureido) -benzamide 3,5-dichloro-2-(N-n-propyl-ureido)-benzamide 1 220 2 (N-rnethoxy-N-methyl-ureido)-benzamide 2-(N ,N-dimethyl-ureido) -benzamide 2-(N,2-methylthio-ethyl-ureido) -benzamide 5-rnethyl-2-(N-rnethyl-ureido)-benzamide 4-meth0xy-2F(N-methyl-ureid0) -benzamide 1 Decomposition.

The production of herbicidal compositions according to the invention is carried out in a manner known per se by the intimate mixing and grinding of the active substances of the general Formula I with suitable carriers, optionally with the addition of dispersion agents or solvents which are inert to the active substances The active substances can exist and be used in the following forms:

As solids: dusts, sprinkling agents, granulates, coated granules, impregnated granules and homogeneous granules;

As concentrates of active substances dispersible in water: wettable powder, pastes, emulsions; as liquids: solutions, aerosols.

To produce the solid forms (dusts, sprinkling agents, granulates) the active substances are mixed with solid carriers. Suitable carriers are, e.g. kaolin, talcum, bole, loess, chalk, limestone, ground limestone, ataclay, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic plastics, fertilisers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas, ground vegetable products such as grain flour, bark flour, sawdust, ground nut shells, cellulose powder, residues of plant extractions, active charcoal, etc. These carriers can be used separately or they can be mixed with each other.

The grain size of the carriers is, for dusts, advantageously up to ca. 0.1 mm., for sprinkling agents it is ca. 0.075 to 0.2 mm. and for granulates 0.2 mm. upwards.

The concentrations of active substances in the solid preparations are, as a rule, 0.5 to of the total weight.

To these mixtures can also be added additives which stabilise the active substance and/or non-ionic, anionactive and cation-active substances, which, for example, improve the adhesion of the active substances on plants and parts of plants (glues and adhesives) and/ or ensure a better wettability (wetting agents) and also dispersibility (dispersing agents). The following are examples of adhesives: olein-chalk mixtures, cellulose derivatives (methyl cellulose, carboxymethy cellulose), hydroxyethyl glycol ethers of monoand dialkyl phenols having 515 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali and alkaline earth metal salts, polyethylene glycol ethers (Carbowaxes), fatty alcohols polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea/formaldehyde as well as latex products.

Concentrates of active substances which can be dispersed in water (wettable powders), pastes and emulsion concentrates, are agents which can be diluted with water 7 to give any desired concentration. They consist of active substances, carriers, optionally additives which stabilise the active substance, surface agent substances and antifoaming agents and, optionally, solvents. The concentration of active substance in these agents is to 80% of the total weight of the latter.

The Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable devices until homogeneity is attained. Suitable carriers are, for example, those previously mentioned for solid preparations. It is advantageous in some cases to use mixtures of different carriers. Suitable dispersing agents are, e.g. condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalene sulphonic acids with phenol and formaldehyde, also alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, also alkylaryl sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl ethionate, the sodium salt of oleyl methyl tauride, ditertiary acetylene glycols, dialkyldilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Examples of anti-foaming agents are: silicones etc. The active substances are so mixed, ground, sieved and strained With the above mentioned additives that the solid particle size in Wettable powders does not exceed 0.02-0.04 mm. and in the case of pastes 0.003 mm. To produce emulsion concentrates and pastes, dispersing agents such as those stated in the previous sections, organic solvents and water are used. Examples of solvents are: alcohols, benzene, xylenes, toluene, dimethyl sulphoxide and mineral oil fractions boiling between 120 and 350 C. The solvents must be practically Without smell, not phytotoxic, inert to the active substances and not easily inflammable.

In addition, the agents according to the invention can be used in the form of solutions. For this application, the active substance or substances of the general Formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, mineral oils, on their own or mixed with each other, can be used as organic solvents. The solvents should contain the active substances within a concentration range of 1 to 20% calculated on the total weight of the resulting solution.

Other biocidal active substances or agents can be mixed with the described compositions according to the invention. Thus in addition to the stated compounds of the general Formula I and other herbicides, the new agents can also contain, e.g. insecticides, fungicides, bactericides, fungistatics, bacteriostatics or nematocides in order to Widen the range of action. The compositions according to the invention can also contain fertilisers, trace elements etc.

Forms of preparation of these active substances are described in the following. Where not otherwise expressly stated, the terms parts and percentages are given by Weight.

Wettable powder The following constituents are used to produce: (a) a Wettable powder, and (b) a 25% Wettable powder:

10 parts of 2-(N'-methylureido)-benzamide 10 parts of lignin sulphonic acid calcium salt 8 2 parts of adhesive consisting of 50% polyvinylpyrrolidone and 50% Champagne chalk 38 parts of kaolin 40 parts of Champagne chalk 25 parts of 2-(N'-ethyl-ureido)-benzamide 5 parts of condensation products of naphthalene sulphonic acid, phenol sulphonic acid and formaldehyde in the ratio 3:2:0.5

4 parts of dibutyl naphthyl sulphonate sodium salt 1 part of methyl-oleyl-tauride sodium salt 15 parts of silicic acid 25 parts of neutral sodium aluminium silicate 25 parts of kaolin The stated active substances are coated on to the corresponding carriers (kaolin and chalk) and then mixed and ground with the listed additives. A Wettable powder is obtained having excellent wettability and suspension properties. Suspensions of any desired active substance concentration can be prepared from this Wettable powder by diluting with water.

Emulsion concentrate The following constituents are mixed together to produce a 25 emulsion concentrate:

25 parts of 2-(N-n-propyl-ureido)-benzamide 35 parts of methyl ethyl ketone 30 parts of xylol and 10 parts of isooctyl-phenyl polyethylene glycol This concentrate can be diluted with Water to obtain emulsions of suitable concentrations. Such emulsions are suitable for controlling weeds in cultivated plantations, for which purpose application of amounts of about 0.5 to 3 kg. of a compound of Formula I per hectare of treated soil is recommended.

R represents hydrogen or lower alkyl,

R represents hydrogen or alkyl of at most 5 carbon atoms,

R represents alkyl, alkenyl or alkynyl of at most 8 carbon atoms; halogen-alkyl of at most 5 carbon atoms; alkoxyalkyl or alkylmercaptoalkyl having at most 5 carbon atoms; or cycloalkyl having from 3 to 10 carbon atoms; and

n represents a Whole number from 0 to 3.

2. 2-(N-methyl-ureido)-benzamide.

References Cited Kiihle, et. al., Justus Liebigs Annalen der Chemie, Band 616, pp. 190-492 (1958).

LEON ZITVER, Primary Examiner M. W. GLYNN, Assistant Examiner US. Cl. X.R. 

